Rapid setting cementitious compositions and method

ABSTRACT

Rapid setting cementitious compositions comprise hydraulic cement and at least 4% by weight based on the weight of the cement of a water-soluble malate or citramalate such as an alkali metal malate or alkali metal citramalate.

This is a continuation of application Ser. No. 08/629,797 filed Apr. 09,1996, now abandoned which is a continuation of application Ser. No.08/309,373, filed Sep. 20, 1994 now abandoned.

The present invention relates to rapid setting cement compositions andmore particularly to the use of certain chemicals as quick-settingagents in formulating such compositions.

Rapid setting cement compositions are desirable and widely usedmaterials, particularly in applications known as lining and reliningconstruction where a continuous layer of modest thickness of a cementcomposition is applied to a surface. A common procedure in which rapidsetting cement compositions are used is well-known as shotcreting. Inall such usages, the cement composition must set quickly in order toretain its position as applied.

The particular quick-setting agent used in rapid-setting cementcompositions will influence a number of performance criteria of interestto the industry. Not only must the agent effect a rapid setting withincertain time limits, but the rapid setting is desirably achieved witheconomically attractive amounts of a quick-setting agent. In addition,the rapid development of strength properties, which does not arisesimply because of the rapid setting, is an important performancecriteria of a quick-setting agent. The ability to continue earlystrength development to a high final strength is also a desirableobjective.

Quick-setting agents have been traditionally strongly alkaline solutionsof silicates and aluminates. The aluminates tend to be better than thesilicates in providing early strength development, but the aluminatesare also caustic. The caustic nature of both the silicates andaluminates has raised both health and environmental concerns.

It is an objective in the cement art to provide alternatives to currentquick-setting agents and particularly to provide quick-setting agentswhich provide rapid early strength development and it would be desirableto have non-caustic agents with such strength development and otherdesired properties.

In accordance with the invention, it has been found that water solublesalts of malic acid (hydroxybutanedioc acid) and citramalic acid(2-hydroxy-2-methylbutanedioc acid), in particular alkali metal salts,are especially useful as quick-setting agents in cementitiouscompositions.

The invention therefore provides in one major aspect thereofrapid-setting cementitious compositions comprising hydraulic cement andat least 4% by weight of the cement of a water soluble salt of malic orcitramalic acid or mixture thereof. These compositions will be appliedin admixture with sufficient water for hydraulic setting of the cement.Both very quick setting and rapid and good strength development areobtained with the invention.

In another embodiment the compositions of the present invention consistessentially of hydraulic cement and at least 4% by weight of the cementof a water soluble salt of malic or citramalic acid or mixture thereof.

A salt of malic acid or citramalic acid for purposes of this inventionis defined as a malic acid or citramalic acid molecule with both oftheir acid groups in salt form, i.e. to provide the disalt forms. Thepreferred water-soluble salt forms are the alkali metal salt forms,particularly the sodium, potassium and lithium salt forms. Theparticularly preferred quick-setting agents are disodium malate,disodium citramalate, dipotassium malate and dipotassium citramalate,and mixtures thereof, with dipotassium malate or dipotassium citramalatebeing most preferred. However, lithium salts may be preferred where thealkali-silica reaction is a concern since it is well known that lithiumsalts inhibit the alkali-silica reaction.

The malic and citramalic acid salts used in the invention are added tothe cementitious compositions in their salt forms which are generallycommercially available. If not commercially available, the salts may beproduced from the commercially available acids. The neutralized acidsare generally added to the cementitious compositions as aqueoussolutions. To achieve the maximum accelerating effect, a solution of theneutralized acid in the mixing water should be added to a mixture of thedry components (cement, aggregate, silica fume, etc.).

In general, at least 4% by weight of water soluble malate based on theweight of the hydraulic cement is required to attain the quick-settingaction possessed by these agents. When a malate is employed in amountsof 4% or more, they will rapidly accelerate the setting of the cement.Substantially greater amounts up to 20% by weight or more may beemployed depending upon the final formulation, objectives and conditionsof use. Desirably, at least 5% water soluble malate or citramalate basedon the weight of the cement is employed with amounts greater than 10%being unnecessary in most applications. Preferably, the amount of malateor citramalate is in the range of 5.0 to 8.5%, more usually 5.5 to 8.0%,based on the weight of the hydraulic cement.

In general, the water soluble malates and citramalates, dependinglargely on the amount employed, can be used to provide quick-setting asdesired in a variety of applications. Hence, an initial setting time ofnot greater than 20 minutes by ASTM Method C266 can be readily achieved.Setting times in the range of 10 seconds to 5 minutes, preferably 30seconds to 5 minutes, as common in shotcreting applications, are easilytargeted by the addition of water soluble malates or citramalates inaccord with the invention.

The hydraulic cement employed in the compositions of the invention is acommercially produced calcium alumino-silicate mineral blend, which whenmixed with water will set to form a hard product. The most common typeof hydraulic cement is portland cement, i.e. types I-IV portland cement,and for purposes of the present invention, portland cement is thepreferred hydraulic cement.

In addition to cement, the compositions of the invention may includeother ingredients commonly present in quick-setting cement compositionsand other cement additives which do not substantially interfere with thequick-setting ability of the compositions of the invention.

A common ingredient of quick-setting cement composition is aggregate,especially fine aggregate such as sand and the like. Pea gravelaggregates (maximum diameter of 0.375 inch) and the like may also beused in shotcrete applications with suitable nozzles. Course aggregatesmay also be used in quick-setting applications. In typical applicationsthe amount of aggregate, e.g. fine aggregate such as silica sand, willbe present in a weight ratio to the cement of from 0.5:1 to 6:1, moreusually from 1.2:1 to 5:1, and particularly from 1.5 to 4.5. Lighterweight aggregates such as perlite and the like may also be used.

A variety of other materials not classed as aggregates may also beincluded. Examples are silica fume, silicones and fibers such as glassand steel fibers. Agents to provide cohesion or bonding of the appliedcement composition, such as polyvinyl alcohols, may also be included.

The amount of water to be included in the quick-setting compositions ofthe invention will vary depending upon the particular application andother known factors, but is always sufficient for the hydraulic settingof the cement component. The amount of water used in shotcreteapplication is usually controlled to avoid undesired fluidity. Hence,the amount of water in shotcrete compositions will usually vary from 20%to 60%, more usually 30% to 45%, by weight of the hydraulic cementcomponent. Since the water soluble malates and citramalates have beenfound to have a solids dispersing effect, the amount of water may beless than that otherwise indicated for particular applications. In otherapplications, greater amounts of water than used in shotcreting may beemployed to provide desired fluidity. Other cement additives to maintainfluidity may also be used but in general the compositions will achieve arapid initial set in not greater than 20 minutes, preferably no morethan 15 minutes under the influence of the water soluble malates orcitramalates when employed in amounts of 4% by weight of the cement orgreater.

The rapid-setting compositions and method of the invention isparticularly useful in shotcrete applications.

Shotcreting can be carried out using a dry mix cement composition (thedry mix system) or a wet mix cement composition (the wet mix system), asdescribed below.

a) The dry mix system is one in which dry mixed cement and aggregate ispneumatically conveyed through a delivery hose and is applied byprojecting it out from the nozzle under pressure; water and a quicksetting agent being added in the vicinity of the nozzle, generallyupstream of the nozzle, just prior to passage into the nozzle. With thissystem it is difficult to control the quantity of water added andtherefore to control the water-cement ratio (hereinafter referred to asthe W/C ratio). Further, dust is generated and this is a drawback.Alternatively the quick setting agent can be added at the point ofmixing instead of vicinal to the nozzle.

b) The wet mix system is a system in which the cement and aggregate aremixed in the presence of water and the mixture pumped through a deliveryhose to a nozzle and then projected pneumatically out of the nozzle; aquick setting agent being added within the nozzle assembly or upstreamof the nozzle just prior to passage into the nozzle. There are alsoexamples of this system where the cement composition can be pumped,rather than pneumatically conveyed, to a point midway between the pointof mixing and the nozzle in the delivery hose followed by pneumaticconveying between this midpoint and nozzle. The system allows goodcontrol of W/C ratio and generates little dust.

Pressures employed in the pneumatic delivery of cement compositions inshotcreting generally range from 60 to 140 psi, and are more usually 80to 120 psi.

A particularly useful method of employing the quick-setting agents ofthe present invention in shotcreting is to add less than an acceleratingamount of a water-soluble salt of malic or citramalic acid initiallyupon batching of the cementitious composition and then to add anadditional accelerating amount of the water-soluble salt of malic acidor citramalic acid in the vicinity of the nozzle, such as described inthe copending application, U.S. Ser. No. (Attorney Docket No.154-0271),filed on the same date as the present application.

If desired, a rheology modifying material capable of impartingthixotropic properties to the cementitious composition may be added asdescribed in the aforementioned U.S. Patent, Ser. No. (Attorney DocketNo.154-0271).

The following examples merely demonstrate the invention and are notintended to limit the same. In the examples, setting time andcompressive strength measurements conform to American Society forTesting and Materials Methods C 266 and C 109, respectively. Allmeasurements were made at room temperature. In the examples set timesare determined from the time the malate or citramalate is mixed with thecement.

EXAMPLE 1

In a plastic bag, 2775 g of mortar mix (dry ingredients), which consistsof 740 g of ordinary portland cement and 2035 g of silica sand, wasblended together. To this mix, 333 g of mixing water will be added.Approximately 50% of the mixing water was placed in the mixing bowl of aHobart lab mixer. The blended dry ingredients were then added. 44.4 g ofdipotassium malate (6% by weight of cement) was dissolved in theremaining mix water and added into the mixing bowl. The mortar was thenmixed for three minutes. The test specimens were then cast immediatelyand determined to have the following properties:

Initial setting time: 7 minutes

Final setting time: 9 minutes

    ______________________________________    Compressive Strength PSI (MPa):    ______________________________________           1 hour                 673 (4.64)           4 hour                 1525 (10.52)           1 day 2739 (18.89)           7 day 4411 (30.42)    ______________________________________

EXAMPLE 2

A mortar mix prepared in strict accord with ASTM C109 was prepared tocontain 8.5% dipotassium malate based on the weight of the cement at awater to cement ratio of 0.45 and was determined to have the followingproperties:

Initial setting time: 4 minutes

Final setting time: 6.5 minutes

    ______________________________________    Compressive Strength PSI (MPa):    ______________________________________           1 hour                 863 (5.95)           4 hour                 1840 (12.69)           1 day 3040 (20.97)           7 day 4081 (28.14)    ______________________________________

EXAMPLE 3

A mortar mix was prepared in strict accord with ASTM C109 and contained8% sodium citramalate based on the weight of cement at a water to cementratio of 0.40 and was determined to have the following set times:

Initial set: 3 minutes

Final set: 5 minutes

We claim:
 1. A quick setting cementitious mixture useful for shotcretingapplications comprising a calcium alumino-silicate mineral blend,wherein said calcium alumino-silicate mineral blend is a hydrauliccement, a water soluble malate or water soluble citramalate, said malateor citramalate being present in an amount effective to accelerate theset of the cementitious mixture, said effective amount being at least5.5% by weight based on the total weight of the calcium alumino-silicatemineral blend.
 2. A composition of claim 1 which includes water for thehydraulic setting time of the cementitious mixture.
 3. A composition ofclaim 2 in which the water soluble malate or citramalate is an alkalimetal malate or alkali metal citramalate.
 4. A composition of claim 3 inwhich the alkali metal malate is dipotassium malate.
 5. A composition ofclaim 1 in which aggregate is included in a weight ratio of aggregate tothe calcium alumino-silicate mineral blend in the range of from 1.2:1 to5:1.
 6. A composition of claim 5 in which the aggregate consists of fineaggregate.
 7. A composition of claim 1 in which the malate orcitramalate is present in an amount of 5.5% to 8.5% by weight based onthe total weight of the calcium alumino-silicate mineral blend.
 8. Arapid-setting cementitious composition for use in shotcretingapplications consisting essentially of a calcium alumino-silicatemineral blend, wherein said calcium alumino-silicate mineral blendcomprises hydraulic cement; a water soluble malate or water solublecitramalate, said malate or citramalate being present in an amounteffective to accelerate the set time of the calcium alumino-silicatecementitious mineral blend, said effective amount being at least 5.5% byweight based on the total weight of the calcium alumino-silicatecementitious mineral blend; water; and optionally at least oneadditional component selected from the group consisting of aggregate,silica fume, silicones, fibers, bonding/cohesive agents, and mixturesthereof.
 9. The composition of claim 8 in which the water soluble malateor water soluble citramalate is an alkali metal malate or alkali metalcitramalate.
 10. The composition of claim 9 in which the alkali metalmalate is selected from the group consisting of dipotassium malate,dipotassium citramalate, disodium malate, disodium citramalate,dilithium malate, and dilithium citramalate.
 11. The composition ofclaim 8 in which aggregate is included in a weight ratio of aggregate tocalcium alumino-silicate cementitious mineral blend in the range of1.2:1 to 5:1.
 12. The composition of claim 11 in which the aggregateconsists of fine aggregate.
 13. The composition of claim 8 in which themalate or citramalate is present in an amount of 5.5% to 8.5% by weightof the calcium alumino-silicate cementitious mineral blend.